pubs.acs.
org/joc
Axially Chiral Bichromophoric Fluorescent Dyes
Heinz Langhals,*,† Alexander Hofer,† Stefan Bernhard,‡
Jay S. Siegel,§ and Peter Mayer†
†
Department of Chemistry, LMU University of Munich,
Butenandtstrasse 13, D-81377 Munich, Germany,
‡
Department of Chemistry, Carnegie Mellon University, 4400
Fifth Avenue, Pittsburgh, Pennsylvania 15213, United States,
and §Institute of Organic Chemistry, University of Zuerich,
Winterthurerstrasse 190, CH-8057 Zurich, Switzerland
Langhals@lrz.uni-muenchen.de
Received November 12, 2010
A new life for Kurt Mislow’s authentic amines: Diami-
nobiphenyls were applied as the framework materials for
the synthesis of axially chiral bichromophoric systems
with strong CD and CPL effects.
Axially chiral diamino binaphtyls and biphenyls were
important compounds for monitoring steric effects and non-
covalent interactions some 50 years ago. Kurt Mislow pre-
pared axially chiral amines in pioneering synthesis on the
basis of bi-o-tolyl and 1,10 -binaphthyl amines.1 On the other
hand, these amines form ideal chiral frameworks for the
construction of multichromophoric devices with restricted
orientation of electronic transition moments where exciton
interactions, charge, and energy transfer become important.
The bi-o-tolyl derivatives are of special interest for such
applications because of their hypsochromic light absorption
avoiding interference with attached chromophores. We in-
vestigated the geometry of (M)-1 by means of X-ray crystal
(1) (a) Mislow, K.; Rutkin, P.; Lazarus, A. K. J. Am. Chem. Soc. 1957, 79,
2974–2975. (b) Jones, W. M.; Wilson, J. W. Tetrahedron Lett. 1965, 21, 1587–
1592. Mislow, K. Angew. Chem. 1958, 70, 638–689. (c) The author J.S.S.
supports the technical aspects of this work fully but disagrees with the use of
terminology like “axial chirality”; see: Mislow, K.; Siegel, J. J. Am. Chem.
Soc. 1984, 106, 3319-3328. Cozzi, F.; Siegel, J. S. Org. Biomol. Chem. 2005,
3, 4296-4298. The author H.L. emphasizes that terms such as “axial
chirality” or the “asymmetric carbon atom” are no more than useful chemical
models for helical arrangements of electrons induced by the nuclear frame-
work. Elements of symmetry of polyatomic molecules in solution are in no
way verified in reality because of zero point vibrations and many other effects
where, for example, phenomenologically achiral molecules form either fast
equilibria of racemization or reach states with rotary alternating axes.
DOI: 10.1021/jo102254a
r XXXX American Chemical Society
FIGURE 1. From left to right: chemical structure, X-ray crystal
structure and calculated (DFT, B3LYP) structure of (M)-1.
structure analysis. The two phenyl groups are nearly ortho-
gonal including an interplanar angle of 85.97(10)°, a dihedral
angle of the nitrogen-attached carbon atoms of -93.95(0)°,
and an interconnecting single bond of 1.493(3) Å; see
Figure 1. The packing of 1 is dominated by weak N-H 3 3 3 N
and N-H 3 3 3 C contacts leading to strands along a. The
structure of 1 was additionally quantum chemically calcu-
lated with the DFT method starting with the geometry from
the X-ray crystal structure analysis and gave a dihedral angle
of -103°; this corresponds to the underestimation2 of steric
interactions by this method. Better results concerning the
crystal structure of 1 were obtained with the semiempirical
AM1 method where -94° was found close to the experi-
mental value.
Perylene-3,4:9,10-tetracarboxylic bisimides3 (2) are suita-
ble chomophores for the construction of bichromophoric
arrangements (dyads) because there is only one electronic
transition in the visible4 helping the interpretation of optical
effects. This very pure π-π* transition in 2 is polarized along
the long molecular axis and is ideal for studying exciton
interactions. High fluorescent quantum yields close to unity,
high molar absorptivities, and chemical and photochemical
stability are further advantages of the chromophore. We
started for the orientation of the chromophores 2 with the
anhydride5 3 where the long-chain sec-alkyl group 1-hexyl-
heptyl renders the material soluble and condensed it with
Mislow’s 2,20 -diamino-4,40 -dimethylbiphenyl1 (1) as the fra-
mework because it exhibits a high barrier for racemization so
(2) (a) Bachrach, S. M. Computational Organic Chemistry; John Wiley &
Sons: New York, 2007; pp 394-395. (b) Villar, R.; Gil, M. J.; Garcia, J. I.;
Martinez-Merino, V. J. Comput. Chem. 2005, 26, 1347–1358. (c) Chem.
Abstr. 2005, 143, 410902. (d) We thank Prof. R. de Vivie-Riedle and Dr.
H.-U. Wagner for helpful discussions.
(3) Reviews: (a) Langhals, H. Helv. Chim. Acta 2005, 88, 1309–1343.
(b) Langhals, H. Heterocycles 1995, 40, 477–500.
(4) Johansson, L. B.-Å.; Langhals, H. Spectrochim. Acta 1991, 47A, 857–861.
(5) (a) Kaiser, H.; Lindner, J.; Langhals, H. Chem. Ber 1991, 124, 529–
535. (b) Kelber, J.; Bock, H.; Thiebaut, O.; Grelet, E.; Langhals, H. Eur. J.
Org. Chem. 2010, DOI: 10.1002/ejoc.201001346.
J. Org. Chem. XXXX, XXX, 000–000 A
JOC Note
FIGURE 2. Calculated structure (DFT, B3LYP) for the N-methyl
derivative of (M)-4.
that both enantiomers (P)-4 and (M)-4 could be obtained as
stable compounds. The barrier of entiomeric stability was
tested for 4 in the solvent Dowtherm A6 where no racemiza-
tion was found at 200 °C for 30 h; the previously reported3,7
binapthyl derivatives exhibited also no racemization under
the same condition. One could estimate a lower limit of
the remarkably high free enthalpy of racemization of >137
kJ 3 mol-1. Furthermore, there was no chemical degradation
of the aliphatic side chains. As a consequence, we tested the
chemical stability by means of DTA and thermogravimetry
at even more elevated temperatures and did not find decom-
position until 380 °C. 26.9% of mass was lost between 380
and 450 °C corresponding to the loss of the aliphatic N subs-
tituents. The aromatic system proved to be stable until 520 °C.
The geometry of (M)-4 was quantum chemically calcu-
lated where a slightly absolutely smaller dihedral angel was
obtained: AM1 -91° and DFT, B3LYP -83°; see Figure 2.
(6) (a) Holser, E. F. J. Ind. Eng. Chem. 1936, 28, 691–698. Chem. Abstr.
1936, 30, 35957. (b) Ullock, D. S.; Gaffert, G. A.; Konz, P. R.; Brown, G. G.
Trans. Am. Inst. Chem. Eng. 1936, 32, 73–86. Chem. Abstr. 1937, 31, 43447.
(c) Rathur, M. A. J. Br. J. Appl. Phys. 1964, 15, 437–438. Chem. Abstr, 1966,
64, 81864.
(7) Langhals, H.; Gold, J. Liebigs Ann./Recl. 1997, 1151–1153.
B J. Org. Chem. Vol. XXX, No. XX, XXXX
Langhals et al.
FIGURE 3. UV/vis absorption, fluorescence (left scale) and CD
spectra (right scale, normal lines) in chloroform. Dashed lines:
Absorption (left) and fluorescence (right) spectra of (M)-4; the
spectra of (P)-4 are identical. Dotted lines: Spectra of 1a (R =
1-hexylheptyl) for comparison. Positive CD effect for (P)-4 and
negative for (M)-4.
This may be a consequence of the interaction of the two
chromophores.
The very small dimethyl biphenyl linker in 4 is of special
advantage compared with the previously published binaph-
thyl spacer7 because it does not contribute to light absorp-
tion in the visible and the UVA. As a consequence, there is no
interference with the light absorption of the perylene chro-
mophore.
The UV/vis absorption spectrum of 4 is strongly struc-
tured and exhibits about two times the absorptivity of 2
except for the most bathochromic band where exciton inter-
action causes a shoulder and the molar absorptivity is dimi-
nished compared with 2. 4 exhibits strong, structured fluo-
rescence being approximately mirror-type concerning the
absorption spectrum (Figure 3).
Fluorescence quantum yields close to unity were found for
both (P)-4 and (M)-4, respectively. There is a precisely
monoexponential decay of fluorescence. The fluorescence
lifetime of 4.54 ns is slightly larger than that for other pery-
lene dyes of about 3.9 ns;3 this corresponds to the compar-
ably smaller molar absorptivity of 4 because 180 000 is
expected for two perylenetetracarboxylic bisimide chromo-
phores, whereas 135 000 was found for 4. Strong mirror-type
CD effects were observed for the enantiomers (P)-4 and (M)-
4, respectively, with Δε of some (500. These are dominated
by exciton interactions because of the very pure π-π*
transition in the perylene chromophores causing as well only
a vanishing CD contribution as the hypsochromic absorp-
tion by the linker. The sign of the exciton interaction
corroborates the reported configuration of the starting
biphenyl amines with respect to the direction of the transi-
tion dipole in the perylene biscarboximides.
2ðΓleft - Γright Þ
g ¼ ð1Þ
Γleft þ Γright
The chirally arranged chromophores emit chiral fluores-
cent light where about 0.1% of the fluorescence was circu-
larly polarized with a comparably strong mirror-type CPL
effect for both enantiomers (Figure 4). Slight deviations from
the complete symmetry are caused by asymmetries of the
experimental setup. Interestingly, there are no strong flips in
sign of the CPL spectra as was observed for the CD spectra in
Langhals et al.
FIGURE 4. Fluorescence CPL spectra (ΔΙ/Ι, thick lines, right scale,
stretched by a factor 2 for better visibility) and g values (- • -) of (M)-
4 (upper lines) and (P)-4 (lower lines) compared with the CD spectra
(dotted lines, left scale; see Figure 2) and the fluorescence spectrum
of (P)-4 (dashed line and arbitrary units).
the absorption. The g value according to eq 1, where Γright
and Γleft respectively mean the intensity of right and left
circularly polarized light, is in the order of 0.2% (cf. Figure 3).
Chiral effects in fluorescence can be attributed to the exciton
interactions, where both CPL and g are in the expected range8,9
for a setup as in 4.
We conclude that atropisomeric diamino biphenyls, initi-
ally introduced for basic investigations of steric effects by
Kurt Mislow, proved to form interesting and powerful
frameworks for the development of novel chiral materials
with unusual optical properties. One could imagine the
construction of a chiral laser-type light amplifier with com-
pounds such as 4 amplifying chiroptical properties.
Experimental Section
CPL Measurements. The previously described10 setup was
applied for CPL.
(P)-4: 9-(1-Hexylheptyl)-2-benzopyrano[60 ,50 ,40 :10,5,6]anthra-
[2,1,9:def]isoquinoline-1,3,8,10-tetraone (2, 85 mg, 0.15 mmol),
(P)-(þ)-6,60 -dimethylbiphenyl-2,20 -diamine (15 mg, 0.07 mmol),
and imidazole (3 g) were heated under argon atmosphere at 140 °C
for 4 h, allowed to cool, still warm precipitated with 2 M aqueous
HCl (20 mL), collected by vacuum filtration (D4 glass filter),
washed with 2 M HCl and distilled water, dried in air at 110 °C for
16 h, and purified by column separation (silica gel, chloroform/
ethanol 50:1). Yield 60 mg (65%) of red solid, mp >300 °C. Rf
(silica gel, chloroform/ethanol 20:1) 0.78. IR (ATR) ν 2921.9 (s),
2855.2 (m), 2361.5 (m), 2337.6 (m), 1697.4 (s), 1656.6 (vs), 1592.0
(vs), 1576.4 (s), 1505.8 (w), 1455.7 (w), 1492.2 (w), 1403.9 (m),
1338.1 (vs), 1250.3 (m), 1172.8 (m), 1124.5 (w), 1105.6 (w), 963.5
(w), 850.8 (w), 809.2 (m), 774.4 (w), 745.1 (w), 681.9 (w), 668.0
cm-1 (w). 1H NMR (600 MHz, CDCl3, 25 °C, TMS) δ 0.74-0.82
(8) (a) Tsumatori, H.; Nakashima, T.; Kawai, T. Org. Lett. 2010, 12,
2362–2365. (b) Tsumatori, H.; Nakashima, T.; Yuasa, J.; Kawai, T. Synth.
Met. 2009, 159, 952–954. (c) Kawai, T.; Kawamura, K.; Tsumatori, H.;
Ishikawa, M.; Naito, M.; Fujiki, M.; Nakashima, T. ChemPhysChem 2007,
8, 1465–1468.
(9) Pritchard, B.; Autschbach, J. ChemPhysChem 2010, 11, 2409–2415.
(10) Oyler, K. D.; Coughlin, F. J.; Bernhard, S. J. Am. Chem. Soc. 2007,
129, 210–217.
JOC Note
(m, 6 H, 2  CH3), 1.02-1.09 (m, 6 H, 2  CH3), 1.12-1.80 (m, 32
H, 16  CH2), 2.22-2.38 (m, 4 H, β-CH2), 2.34-2.56 (m, 4 H, β-
CH2), 2.73 (s, 6 H, 2  CH3), 5.25-5.36 (m, 2 H, NCH), 7.18 (d,
3
J(H,H) = 6.5 Hz, 2 H, 2  CHaromat.), 7.39 (t, 3J(H,H) = 7.5 Hz,
2 H, 2  CHaromat.), 7.79 (d, 3J(H,H) = 6.8 H, 2 H, 2  CHaromat.),
8.20-8.79 ppm (m, 16 H, 16  CHperylene). 13C NMR (150 MHz,
CDCl3, 25 °C, TMS) δ 14.0, 14.3, 20.5, 22.5, 22.9, 26.9, 27.0, 27.4,
27.6, 29.2, 29.5, 29.7, 31.7, 32.0, 32.9, 33.1, 122.5, 123.0, 124.0,
124.7, 125.9, 126.0, 127.1, 128.5, 129.2, 130.2, 131.4, 132.3, 134.1,
134.4, 134.5, 134.8, 135.9, 141.7, 162.9, 163.8, 164.6 ppm. UV/vis
(CHCl3) λmax (ε) 461.3 (36 400), 492.1 (100 400), 535.7 nm
(134 500). Fluorescence (CHCl3) λmax (Irel) 542.0 (1.00), 585.0
(0.44), 635.0 nm (0.10). Fluorescence quantum yield (CHCl3,
λexc = 585 nm, E585 nm/1 cm = 0.0155, reference: 1 with Φ =
1.00) 1.00. MS (FABþ) m/z (%) 1323.6 (0.6) [Mþ þ H], 1322.6
(0.3) [Mþ]. HRMS (C87H81N4O8) calcd m/z 1322.6133, found m/z
1322.6117; Δ = þ0.0016. Anal. Calcd for C87H81N4O8 (1322.6):
C 79.85, H 6.24, N 4.23. Found: C 79.56, H 6.33, N 4.16.
(M)-4: 9-(1-Hexylheptyl)-2-benzopyrano[60 ,50 ,40 :10,5,6]anthra-
[2,1,9:def]isoquinoline-1,3,8,10-tetraone (2, 284 mg, 0.495 mmol),
(M)-(-)-6,60 -dimethylbiphenyl-2,20 -diamine (50.0 mg, 0.236 mmol),
and imidazole (5 g) were allowed to react and purified as was
described for (P)-4. Yield 201 mg (65%) of red solid, mp >300 °C.
Rf (silica gel, chloroform/ethanol 20:1) 0.78. IR (ATR) ν 2921.9
(s), 2855.2 (m), 2361.5 (m), 2337.6 (m), 1697.4 (s), 1656.6 (vs),
1592.0 (vs), 1576.4 (s), 1505.8 (w), 1455.7 (w), 1492.2 (w), 1403.9
(m), 1338.1 (vs), 1250.3 (m), 1172.8 (m), 1124.5 (w), 1105.6 (w),
963.5 (w), 850.8 (w), 809.2 (m), 774.4 (w), 745.1 (w), 681.9 (w),
668.0 cm-1 (w). 1H NMR (600 MHz, CDCl3, 25 °C, TMS) δ
0.74-0.82 (m, 6 H, 2  CH3), 1.02-1.11 (m, 6 H, 2  CH3),
1.12-1.88 (m, 32 H, 16  CH2), 2.22-2.39 (m, 4 H, β-CH2),
2.35-2.49 (m, 4 H, β-CH2), 2.70 (s, 6 H, 2  CH3), 5.26-5.33 (m,
2 H, NCH), 7.16 (d, 3J(H,H) = 6.5 Hz, 2 H, 2  CHaromat.),
7.37 (t, 3J(H,H) = 7.5 Hz, 2 H, 2  CHaromat.), 7.75 (d, 3J(H,H) =
6.8 H, 2 H, 2  CHaromat.), 8.20-8.79 ppm (m, 16 H, 16 
CHperylene.). 13C NMR (150 MHz, CDCl3, 25 °C, TMS) δ 14.0,
14.3, 20.5, 22.5, 22.9, 26.9, 27.0, 27.4, 27.6, 29.2, 29.5, 29.7, 31.7,
32.0, 32.9, 33.1, 122.5, 123.0, 124.0, 124.7, 125.9, 126.0, 127.1,
128.5, 129.2, 130.2, 131.4, 132.3, 134.1, 134.4, 134.5, 134.8, 135.9,
141.7, 162.9, 163.8, 164.6 ppm. UV/vis (CHCl3) λmax (ε) 461.3
(36 400), 492.1 (100 400), 535.7 nm (134 500). Fluorescence
(CHCl3) λmax (Irel) = 542.0 (1.00), 585.0 (0.44), 635.0 nm (0.10).
Fluorescence quantum yield (CHCl3, λexc = 585 nm, E585 nm/1 cm =
0.0155, reference: 1 with Φ = 1.00) 1.00. MS (FABþ) m/z (%)
1323.1 (0.8) [Mþ þ H], 1322.1 (0.5) [Mþ]. HRMS (C87H81N4O8)
calcd m/z 1322.6133, found m/z 1322.6228; Δ = þ0.0095. Anal.
Calcd for C87H81N4O8 (1322.6): C 79.85, H 6.24, N 4.23. Found:
C 79.47, H 6.26, N 4.15.
Acknowledgment. We thank the Fonds der Chemischen
Industrie and the CIPSM cluster in Munich for financial
support and Kurt Mislow for a gift of the authentic amines
(P)-1 and (M)-1. S.B. gratefully acknowledges support
through an NSF CAREER Award (CHE-0949238).
Supporting Information Available: Crystallographic data of
(M)-1, 1H NMR and 13C NMR of compounds (M)-1, (P)-4, and
(M)-4, the measurement of the fluorescence lifetime of (M)-4,
stability of the configuration of (P)-4, and the thermal stability
of (P)-4 by DTA (differential thermoanalysis) and TGA
(thermogravimetry). This material is available free of charge
via the Internet at http://pubs.acs.org.
J. Org. Chem. Vol. XXX, No. XX, XXXX C